The coupled atmospheric reaction-vacuum distillation technology with benzyl chloride as raw material was set up to obtain high selectivity of benzal chloride.The inside-outside method based on the Newton-Raphson method was correspondingly set up to simulate the process.Furthermore,the effects of the configuration parameters,such as the number of stripping stages,the number of separation stages between adjacent reactors and the number of reactors,and the operating parameters,such as the feed flow rate of chlorine with its distributed ratios to the reactors,on the purity of benzal chloride at the bottoms were investigated to select the suitable process parameters.Results demonstrated that,for the novel process,in which the reactor temperature was set to 100 ℃ and the column pressure was fixed at 10 kPa,the suitable choices of the number of stripping stages,the number of separation stages in the reaction zone and the number of reactors were 15,1, and 3,respectively. Besides,when the vapor boilup rate was 10 kmol/h and the distributed ratios of chlorine to the reactors were 0.34,0.33, and 0.33,with the decreasing feed flow rate of chlorine,the purity of benzal chloride at the bottoms was obviously increased and even a high purity above 0.99 was obtained.